Method for producing β-ketoenol esters

ABSTRACT

The invention relates to a method for producing β-ketoenol esters of the general formula (Ia) or (Ib), wherein Ar, R a  and R b  are defined as in claim  1 . The inventive method is characterized by reacting an arylhalogenide of the general formula (II) with a 1,3-diketone of the general formula (III) or the tautomers thereof in a carbon monoxide atmosphere in the presence of an alkali and a catalyst that contains at least one transition metal of group VIII of the periodic system

The present invention relates to a process for preparing β-ketoenolesters of the formulae Ia and Ib

in which

-   R^(a), R^(b) independently of one another are C₁-C₆-alkyl or    C₃-C₈-cycloalkyl, or-   R^(a) and R^(b) together are C₂-C₄-alkanediyl or    C₅-C₇-cycloalkanediyl, where the three groups mentioned above may be    substituted or unsubstituted and may have a fused 3-, 4-, 5- or    6-membered saturated carbocycle, a spiro-linked 3-, 4-, 5- or 6- or    7-membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or    7-membered saturated heterocycle having 1 or 2 chalkogen atoms,    selected from the group consisting of oxygen and sulfur and/or a    carbonyl or thiocarbonyl group;-   Ar is phenyl or pyridyl, which may in each case have 1, 2, 3 or 4    substituents, it also being possible for two substituents attached    to adjacent carbon atoms to form, together with these atoms, a 5- or    6-membered saturated or unsaturated carbocycle or a 5- or 6-membered    saturated or unsaturated heterocycle which has 1, 2 or 3 hetero    atoms selected from the group consisting of O, N and S and which for    its part may be substituted or unsubstituted.

β-Ketoenol esters of aromatic carboxylic acids which correspond to theformulae Ia and Ib defined above are interesting intermediates forpreparing herbicidally active 2-aroyl-1,3-diketones of the formula X:

in which R^(a), R^(b) and Ar are as defined above.

Herbicidallly active 2-aroyl-1,3-diketones are disclosed, for example,in EP-A 90262, EP-A 135191, EP-A 162166, EP-A 186118, EP-A 186119, EP-A283261, EP-A 319075, WO 90/05712, WO 94/04524, WO 94/08988, JP 3052862,JP 3120202, WO 96/04182, WO 97/09324, WO 99/03845 and Weed Science, 45(1997), 601-609 and the literature cited therein.

The 2-aroyl-1,3-diketones are generally prepared starting with anaromatic carboxylic acid of the formula Ar—COOH or its acyl chlorideAr—CO—Cl, which is reacted with a 1,3-diketone of the formula IIIR^(a)—C(O)—CH₂—C(O)—R^(b)  (III)or its tautomer III′ or III″R^(a)—C(O)—CH═C(OH—)—R^(b)  (III′);R^(a)—C(OH)═CH—C(O)—R^(b)  (III″)in which R^(a) and R^(b) are as defined above in the presence of adehydrating agent, for example an anhydride or a carbodiimide, to giveβ-ketoenol esters of the formula I defined above.

The β-ketoenol esters I are then rearranged with a base, preferably inthe presence of a catalytically effective amount of acyanide-group-containing compound, to give the herbicidally active2-aroyl-1,3-diketones of the formula X defined above. In place of thecarboxylic acid Ar—COOH, it is also possible to employ an activated arylcarboxylic acid derivative, for example a carbonyl halide Ar—COL, inwhich L is a halogen atom, such as chlorine, for preparing β-ketoenolesters I. The reaction of the acid halide with III to give I ispreferably carried out in the presence of a base (cf. the abovementionedprior art, in particular EP 283261 and WO 96/05182, and the literaturecited therein).

This process has the disadvantage that the aromatic carboxylic acidsAr—COOH have to be prepared in a complicated manner, for example fromthe more easily accessible aryl halides, for example by successiveconversion into an organometallic compound and subsequent reaction withCO₂, or by side-chain oxidation of ethyl-substituted aromatics.

In particular in the case of aromatic compounds having fusedheterocycles, the preparation of the carboxylic acids Ar—COOH is notwithout problems. The subsequent reaction of the arylcarboxylic acidsAr—COOH or their activated derivatives Ar—COL into the β-ketoenol estersI can likewise not always be realized with satisfactory yields.

It is an object of the present invention to provide a more economicalprocess for preparing β-ketoenol esters of the formula I.

We have found that this object is achieved by reacting aryl halides ofthe formula IIAr-Hal  (II)in which Ar is as defined above and Hal is a halogen atom selected fromthe group consisting of chlorine, bromine and iodine with a 1,3-diketoneof the formula III or its tautomer III′ or III″ in a carbon monoxideatmosphere in the presence of a base and a catalyst which comprises atleast one transition metal of group VIII of the Periodic Table of theElements, which, surprisingly, gives the β-ketoenol esters of theformula I defined above in good yields.

Accordingly, the present invention relates to a process for preparingβ-ketoenol esters of the formula Ia or Ib defined at the outset, whichprocess comprises reacting an aryl halide of the formula II definedabove with a 1,3-diketone of the formula III or its tautomer III′ orIII″ in a carbon monoxide atmosphere in the presence of a base and acatalyst which comprises at least one transition metal of group VIII ofthe Periodic Table of the Elements.

The present invention furthermore relates to a process in whichinitially an aryl halide of the formula II is reacted with a1,3-diketone of the formula III or its tautomer III′ or III″ in a carbonmonoxide atmosphere in the presence of the base and a catalyst whichcomprises at least one transition metal of group VIII of the PeriodicTable of the Elements to give a β-ketoenol ester of the formula Ia or Ibdefined at the outset, and then rearranging this β-ketoenol ester bytreatment with a base and a catalytically effective amount of at leastone cyanide compound into 2-aryl-substituted 1,3-diketones of theformula X or their tautomers Xa, Xb or Xc.

The organic molecular moieties mentioned for the substituents R^(a),R^(b) and Ar or below as radicals on phenyl and heterocyclyl radicalsare collective terms for individual enumerations of the individual groupmembers. All hydrocarbon chains, i.e. all alkyl, haloalkyl, alkoxy,haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl,N-alkylamino, N,N-dialkylamino, alkylcarbonyl, alkoxycarbonyl,alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyalkyl,alkoxyiminoalkyl, phenylalkyl, heterocyclylalkyl, alkenylcarbonyl,alkenyloxycarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl,alkenyloxy, alkynyloxy, alkanediyl, alkenediyl, alkanediendiyl oralkyndiyl moieties can be straight-chain or branched. The termC_(n)-C_(m) indicates the number of possible carbon atoms. Unlessindicated otherwise, halogenated substituents preferably carry one tofive identical or different halogen atoms. The term halogen denotes ineach case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

-   -   C₁-C₄-alkyl and the alkyl moieties of (di)-C₁-C₄-alkylamino,        C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,        C₁-C₄-alkylsulfonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl,        C₁-C₄-alkyloxycarbonyl, C₁-C₄-alkylaminocarbonyl,        C₁-C₄-alkylcarbonylamino: for example methyl, ethyl, propyl,        1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or        1,1-dimethylethyl;    -   C₁-C₆-alkyl, and the alkyl moieties of (di)-C₁-C₆-alkylamino,        C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl,        C₁-C₆-alkylsulfonyl, C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxycarbonyl,        C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkylaminocarbonyl,        C₁-C₆-alkylcarbonylamino: C₁-C₄-alkyl, as mentioned above, and        also, for example, pentyl, 1-methylbutyl, 2-methylbutyl,        3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,        1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,        2-methylpentyl, 3-methylpentyl, 4-methylpentyl,        1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,        2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,        1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,        1-ethyl-1-methylpropyl or 1-ethyl-3-methylpropyl;    -   C₁-C₄-haloalkyl and the haloalkyl moieties of        (di)-C₁-C₄-haloalkylamino, C₁-C₄-haloalkoxy,        C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulfinyl,        C₁-C₄-haloalkylsulfonyl, C₁-C₄-haloalkylcarbonyl,        C₁-C₄-haloalkoxycarbonyl, C₁-C₄-haloalkyloxycarbonyl,        C₁-C₄-haloalkylaminocarbonyl, C₁-C₄-haloalkylcarbonylamino: a        C₁-C₄-alkyl radical as mentioned above which is partially or        fully substituted by fluorine, chlorine, bromine and/or iodine,        i.e., for example, chloromethyl, dichloromethyl,        trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,        chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,        2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,        2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,        2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,        2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl,        3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,        2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl,        2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,        3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl,        heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl,        1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,        4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;    -   C₁-C₆-haloalkyl, and the haloalkyl moieties of        (di)-C₁-C₆-haloalkylamino, C₁-C₆-haloalkoxy,        C₁-C₆-haloalkylthio, C₁-C₆-haloalkylsulfinyl,        C₁-C₆-haloalkylsulfonyl, C₁-C₆-haloalkylcarbonyl,        C₁-C₆-haloalkoxycarbonyl, C₁-C₆-haloalkyloxycarbonyl,        C₁-C₆-haloalkylaminocarbonyl, C₁-C₆-haloalkylcarbonylamino:        C₁-C₄-haloalkyl as mentioned above, and also, for example,        5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl,        undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl,        6-iodinehexyl or dodecafluorohexyl;    -   C₁-C₄-alkoxy: for example methoxy, ethoxy, propoxy,        1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or        1,1-dimethylethoxy;    -   C₁-C₆-alkoxy: C₁-C₄-alkoxy as mentioned above, and also, for        example, pentoxy, 1-methylbutoxy, 2-methylbutoxy,        3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,        2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy,        2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,        1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,        2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,        1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,        1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or        1-ethyl-2-methylpropoxy;    -   C₁-C₆-haloalkoxy: a C₁-C₆-alkoxy radical as mentioned above        which is partially or fully substituted by fluorine, chlorine,        bromine and/or iodine;    -   C₁-C₆-alkylcarbonyl, and the alkylcarbonyl radicals of        C₁-C₆-alkylcarbonyl-C₁-C₆-alkyl, C₁-C₆-alkylcarbonyloxy,        C₁-C₆-alkylcarbonylamino: an alkyl radical which is attached via        a carbonyl group, for example methylcarbonyl, ethylcarbonyl,        propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl,        1-methylpropylcarbonyl, 2-methylpropylcarbonyl,        1,1-dimethylethylcarbonyl;    -   C₁-C₄-alkoxycarbonyl: for example methoxycarbonyl,        ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl,        butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl        or 1,1-dimethylethoxycarbonyl;    -   C₁-C₆-alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl,        propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl,        1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or        1,1-dimethylethoxycarbonyl, pentoxycarbonyl,        1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl,        3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl,        1-ethylpropoxycarbonyl, hexoxycarbonyl,        1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl,        1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl,        3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl,        1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl,        1,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl,        2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl,        1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl,        1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl,        1-ethyl-1-methylpropoxycarbonyl or        1-ethyl-2-methylpropoxycarbonyl;    -   (C₁-C₄-alkyl)carbonyloxy: acetyloxy, ethylcarbonyloxy,        propylcarbonyloxy, 1-methylethylcarbonyloxy, butylcarbonyloxy,        1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy or        1,1-dimethylethylcarbonyloxy;    -   C₁-C₆-hydroxyalkyl: C₁-C₆-alkyl which is substituted by one to        three OH— groups, for example hydroxymethyl, 1-hydroxyethyl,        2-hydroxyethyl, 1,2-bishydroxyethyl, 1-hydroxypropyl,        2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl,        2,2-dimethyl-3-hydroxypropyl;    -   C₁-C₆-hydroxyalkoxy: C₁-C₆-alkoxy which is substituted by one to        three OH— groups, for example hydroxymethoxy, 1-hydroxyethoxy,        2-hydroxyethoxy, 1,2-bishydroxyethoxy, 1-hydroxypropoxy,        2-hydroxypropoxy, 3-hydroxypropoxy, 4-hydroxybutoxy,        2,2-dimethyl-3-hydroxypropoxy;    -   phenyl-C₁-C₆-alkyl: C₁-C₆-alkyl which is substituted by a phenyl        radical, for example benzyl, 1-phenylethyl and 2-phenylethyl,        where the phenyl radical may, in the manner mentioned above, be        partially or fully halogenated and/or may carry one to three of        the substituents mentioned above for phenyl;        -   correspondingly, heterocyclyl C₁-C₆-alkyl is a C₁-C₆-alkyl            which is substituted by a heterocyclyl radical;    -   C₁-C₆-alkoxy-C₁-C₆-alkyl: C₁-C₆-alkyl which is substituted by        C₁-C₆-alkoxy as mentioned above, i.e., for example,        methoxymethyl, ethoxymethyl, propoxymethyl,        (1-methylethoxy)methyl, butoxymethyl, (1-methylpropoxy)methyl,        (2-methylpropoxy)methyl, (1,1-dimethylethoxy)methyl,        2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(propoxy)ethyl,        2-(1-methylethoxy)ethyl, 2-(butoxy)ethyl,        2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl,        2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl,        2-(ethoxy)propyl, 2-(propoxy)propyl, 2-(1-methylethoxy)propyl,        2-(butoxy)propyl, 2-(1-methylpropoxy)propyl,        2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl,        3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(propoxy)propyl,        3-(1-methylethoxy)propyl, 3-(butoxy)propyl,        3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl,        3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl,        2-(propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(butoxy)butyl,        2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl,        2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl,        3-(propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(butoxy)butyl,        3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl,        3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl,        4-(propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(butoxy)butyl,        4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or        4-(1,1-dimethylethoxy)butyl;    -   di-(C₁-C₆-alkoxy)methyl: methyl which is substituted by two        C₁-C₆-alkoxy groups;    -   di-(C₁-C₆-alkylthio)methyl: methyl which is substituted by two        C₁-C₆-alkylthio groups;    -   (C₁-C₆-alkoxy)(C₁-C₆-alkylthio)methyl: methyl which is        substituted by one C₁-C₆-alkoxy group and by one C₁-C₆-alkylthio        group;    -   C₁-C₆-(halo)alkylsulfonyl-C₁-C₆-alkyl,        C₁-C₆-(halo)alkylthio-C₁-C₆-alkyl, C₁-C₆-alkylamino-C₁-C₆-alkyl,        di-C₁-C₆-alkylamino-C₁-C₆-alkyl: C₁-C₆-alkyl which is        substituted by C₁-C₆-(halo)alkylsulfonyl, C₁-C₆-(halo)alkylthio,        C₁-C₆-alkylamino and di-C₁-C₆-alkylamino respectively;    -   C₁-C₆-alkoxy-C₁-C₆-alkoxy: C₁-C₆-alkoxy, which is substituted by        C₁-C₆-alkoxy as mentioned above, i.e., for example,        methoxymethoxy, ethoxymethoxy, propoxymethoxy,        (1-methylethoxy)methoxy, butoxymethoxy,        (1-methylpropoxy)methoxy, (2-methylpropoxy)methoxy,        (1,1-dimethylethoxy)methoxy, 2-(methoxy)ethoxy,        2-(ethoxy)ethoxy, 2-(propoxy)ethoxy, 2-(1-methylethoxy)ethoxy,        2-(butoxy)ethoxy, 2-(1-methylpropoxy)ethoxy,        2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethylethoxy)ethoxy,        2-(methoxy)propoxy, 2-(ethoxy)propoxy, 2-(propoxy)propoxy,        2-(1-methylethoxy)propoxy, 2-(butoxy)propoxy,        2-(1-methylpropoxy)propoxy, 2-(2-methylpropoxy)propoxy,        2-(1,1-dimethylethoxy)propoxy, 3-(methoxy)propoxy,        3-(ethoxy)propoxy, 3-(propoxy)propoxy,        3-(1-methylethoxy)propoxy, 3-(butoxy)propoxy,        3-(1-methylpropoxy)propoxy, 3-(2-methylpropoxy)propoxy,        3-(1,1-dimethylethoxy)propoxy, 2-(methoxy)butoxy,        2-(ethoxy)butoxy, 2-(propoxy)butoxy, 2-(1-methylethoxy)butoxy,        2-(butoxy)butoxy, 2-(1-methylpropoxy)butoxy,        2-(2-methylpropoxy)butoxy, 2-(1,1-dimethylethoxy)butoxy,        3-(methoxy)butoxy, 3-(ethoxy)butoxy, 3-(propoxy)butoxy,        3-(1-methylethoxy)butoxy, 3-(butoxy)butoxy,        3-(1-methylpropoxy)butoxy, 3-(2-methylpropoxy)butoxy,        3-(1,1-dimethylethoxy)butoxy, 4-(methoxy)butoxy,        4-(ethoxy)butoxy, 4-(propoxy)butoxy, 4-(1-methylethoxy)butoxy,        4-(butoxy)butoxy, 4-(1-methylpropoxy)butoxy,        4-(2-methylpropoxy)butoxy or 4-(1,1-dimethylethoxy)butoxy;    -   C₁-C₆-alkylcarbonyl-C₁-C₆-alkyl: C₁-C₆-alkyl which is        substituted by a C₁-C₆-alkylcarbonyl group, where both of the        C₁-C₆-alkyl groups may carry one or more substituents selected        from the group consisting of C₁-C₄-alkoxy and hydroxyl: for        example acetylmethyl(=2-oxopropyl), 2-(acetyl)ethyl        (=3-oxo-n-butyl), 3-oxo-n-pentyl, 1,1-dimethyl-2-oxopropyl,        3-hydroxy-2-oxopropyl or 3-hydroxy-2-oxobutyl;    -   C₃-C₆-alkenyl, and the alkenyl moieties of C₃-C₆alkenylcarbonyl,        C₃-C₆-alkenyloxy, C₃-C₆-alkenyloxycarbonyl,        C₃-C₆-alkenylaminocarbonyl,        N—(C₃-C₆-alkenyl)-N—(C₁-C₆-alkyl)aminocarbonyl,        N—(C₃-C₆-alkenyl)-N—(C₁-C₆-alkoxy)aminocarbonyl: for example        prop-2-en-1-yl, but-1-en-4-yl, 1-methylprop-2-en-1-yl,        2-methylprop-2-en-1-yl, 2-buten-1-yl, 1-penten-3-yl,        1-penten-4-yl, 2-penten-4-yl, 1-methylbut-2-en-1-yl,        2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl,        1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl,        3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl,        1,2-dimethylprop-2-en-1-yl, 1-ethylprop-2-en-1-yl,        hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl,        1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,        3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl,        1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl,        3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,        1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,        1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl,        1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,        2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-2-en-1-yl,        2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-2-en-1-yl,        1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,        2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,        1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl or        1-ethyl-2-methylprop-2-en-1-yl;    -   C₂-C₆-alkenyl, and the alkenyl moieties of        C₂-C₆-alkenylcarbonyl, phenyl-C₂-C₆-alkenylcarbonyl and        heterocyclyl-C₂-C₆-alkenylcarbonyl: C₃-C₆-alkenyl, as mentioned        above, and also ethenyl;    -   C₃-C₆-alkynyl, and the alkynyl moieties of        C₃-C₆-alkynylcarbonyl, C₃-C₆-alkynyloxy,        C₃-C₆-alkynyloxycarbonyl, C₃-C₆-alkynylaminocarbonyl,        N—(C₃-C₆-alkynyl)-N—(C₁-C₆-alkyl)aminocarbonyl,        N—(C₃-C₆-alkynyl)-N—(C₁-C₆-alkoxy)aminocarbonyl: for example        propargyl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl,        pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl,        pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl,        3-methylbut-1-yn-4-yl, hex-1-yn-3-yl, hex-1-yn-4-yl,        hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl,        hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl,        3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,        3-methylpent-1-yn-5-yl, 4-methylpent-2-yn-4-yl or        4-methylpent-2-yn-5-yl;    -   C₂-C₆-alkynyl, and the alkynyl moieties of        C₂-C₆-alkynylcarbonyl: C₃-C₆-alkynyl as mentioned above, and        also ethynyl;    -   C₂-C₄-alkanediyl for R^(a) and R^(b): ethane-1,2-diyl,        propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl,        butane-1,3-diyl, butane-1,4-diyl, in particular        propane-1,3-diyl;    -   C₁-C₆-alkanediyl: methanediyl, ethane-1,1-diyl, ethane-1,2-diyl,        propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl,        propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl,        butane-1,3-diyl, butane-1,4-diyl, 2-methylpropane-1,3-diyl,        2-methylpropane-1,2-diyl, 2-methylpropane-1,1-diyl,        1-methylpropane-1,2-diyl, 1-methylpropane-2,2-diyl,        1-methylpropane-1,1-diyl, pentane-1,1-diyl, pentane-1,2-diyl,        pentane-1,3-diyl, pentane-1,5-diyl, pentane-2,3-diyl,        pentane-2,2-diyl, 1-methylbutane-1,1-diyl,        1-methylbutane-1,2-diyl, 1-methylbutane-1,3-diyl,        1-methylbutane-1,4-diyl, 2-methylbutane-1,1-diyl,        2-methylbutane-1,2-diyl, 2-methylbutane-1,3-diyl,        2-methylbutane-1,4-diyl, 2,2-dimethylpropane-1,1-diyl,        2,2-dimethylpropane-1,3-diyl, 1,1-dimethylpropane-1,3-diyl,        1,1-dimethylpropane-1,2-diyl, 2,3-dimethylpropane-1,3-diyl,        2,3-dimethylpropane-1,2-diyl, 1,3-dimethylpropane-1,3-diyl,        hexane-1,1-diyl, hexane-1,2-diyl, hexane-1,3-diyl,        hexane-1,4-diyl, hexane-1,5-diyl, hexane-1,6-diyl,        hexane-2,5-diyl, 2-methylpentane-1,1-diyl,        1-methylpentane-1,2-diyl, 1-methylpentane-1,3-diyl,        1-methylpentane-1,4-diyl, 1-methylpentane-1,5-diyl,        2-methylpentane-1,1-diyl, 2-methylpentane-1,2-diyl,        2-methylpentane-1,3-diyl, 2-methylpentane-1,4-diyl,        2-methylpentane-1,5-diyl, 3-methylpentane-1,1-diyl,        3-methylpentane-1,2-diyl, 3-methylpentane-1,3-diyl,        3-methylpentane-1,4-diyl, 3-methylpentane-1,5-diyl,        1,1-dimethylbutane-1,2-diyl, 1,1-dimethylbutane-1,3-diyl,        1,1-dimethylbutane-1,4-diyl, 1,2-dimethylbutane-1,1-diyl,        1,2-dimethylbutane-1,2-diyl, 1,2-dimethylbutane-1,3-diyl,        1,2-dimethylbutane-1,4-diyl, 1,3-dimethylbutane-1,1-diyl,        1,3-dimethylbutane-1,2-diyl, 1,3-dimethylbutane-1,3-diyl,        1,3-dimethylbutane-1,4-diyl, 1-ethylbutane-1,1-diyl,        1-ethylbutane-1,2-diyl, 1-ethylbutane-1,3-diyl,        1-ethylbutane-1,4-diyl, 2-ethylbutane-1,1-diyl,        2-ethylbutane-1,2-diyl, 2-ethylbutane-1,3-diyl,        2-ethylbutane-1,4-diyl, 2-ethylbutane-2,3-diyl,        2,2-dimethylbutane-1,1-diyl, 2,2-dimethylbutane-1,3-diyl,        2,2-dimethylbutane-1,4-diyl, 1-isopropylpropane-1,1-diyl,        1-isopropylpropane-1,2-diyl, 1-isopropylpropane-1,3-diyl,        2-isopropylpropane-1,1-diyl, 2-isopropylpropane-1,2-diyl,        2-isopropylpropane-1,3-diyl, 1,2,3-trimethylpropane-1,1-diyl,        1,2,3-trimethylpropane-1,2-diyl or        1,2,3-trimethylpropane-1,3-diyl;    -   C₃-C₈-cycloalkyl, and the cycloalkyl moieties of        C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylamino and        C₃-C₈-cycloalkylcarbonyl: for example cyclopropyl, cyclobutyl,        cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl,        [2.2.2]- or [3.2.1]bicyclooctyl;    -   C₅-C₇-cycloalkanediyl for R^(a) and R^(b): a divalent        cycloaliphatic radical having 5 to 7 ring carbons, for example        cyclopentane-1,2-diyl or -1,3-diyl, cyclohexane-1,2-diyl,        -1,3-diyl or -1,4-diyl, cycloheptane-1,2-diyl, -1,3-diyl or        -1,4-diyl;    -   5- to 7-membered heterocyclyl, and heterocyclyl moieties and        fused 5- or 6-membered heterocycles on phenyl or pyridyl: a        saturated, partially saturated or unsaturated 5-, 6- or        7-membered heterocyclic ring which contains one, two, three or        four identical or different heteroatoms selected from the group        consisting of oxygen, sulfur and nitrogen and which, in the case        of the fused heterocycles, has at least one C═C double bond,        i.e., for example,    -   C-bonded 5-membered rings, such as:        -   tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,            tetrahydrothien-2-yl, tetrahydrothien-3-yl,            tetrahydropyrrol-2-yl, tetrahydropyrrol-3-yl,            2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl,            2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl,            4,5-dihydrofuran-2-yl, 4,5-dihydrofuran-3-yl,            2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,            2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl,            4,5-dihydrothien-2-yl, 4,5-dihydrothien-3-yl,            2,3-dihydro-1H-pyrrol-2-yl, 2,3-dihydro-1H-pyrrol-3-yl,            2,5-dihydro-1H-pyrrol-2-yl, 2,5-dihydro-1H-pyrrol-3-yl,            4,5-dihydro-1H-pyrrol-2-yl, 4,5-dihydro-1H-pyrrol-3-yl,            3,4-dihydro-2H-pyrrol-2-yl, 3,4-dihydro-2H-pyrrol-3-yl,            3,4-dihydro-5H-pyrrol-2-yl, 3,4-dihydro-5H-pyrrol-3-yl,            2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl,            pyrrol-3-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl,            tetrahydroisoxazol-3-yl, tetrahydroisoxazol-4-yl,            tetrahydroisoxazol-5-yl, 1,2-oxathiolan-3-yl,            1,2-oxathiolan-4-yl, 1,2-oxathiolan-5-yl,            tetrahydroisothiazol-3-yl, tetrahydroisothiazol-4-yl,            tetrahydroisothiazol-5-yl, 1,2-dithiolan-3-yl,            1,2-dithiolan-4-yl, tetrahydroimidazol-2-yl,            tetrahydroimidazol-4-yl, tetrahydrooxazol-2-yl,            tetrahydrooxazol-4-yl, tetrahydrooxazol-5-yl,            tetrahydrothiazol-2-yl, tetrahydrothiazol-4-yl,            tetrahydrothiazol-5-yl, 1,3-dioxolan-2-yl,            1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl,            1,3-oxathiolan-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl,            4,5-dihydro-1H-pyrazol-3-yl, 4,5-dihydro-1H-pyrazol-4-yl,            4,5-dihydro-1H-pyrazol-5-yl, 2,5-dihydro-1H-pyrazol-3-yl,            2,5-dihydro-1H-pyrazol-4-yl, 2,5-dihydro-1H-pyrazol-5-yl,            4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl,            4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl,            2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-5-yl,            2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl,            2,3-dihydroisoxazol-5-yl, 4,5-dihydroisothiazol-3-yl,            4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl,            2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl,            2,5-dihydroisothiazol-5-yl, 2,3-dihydroisothiazol-3-yl,            2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl,            Δ³-1,2-dithiol-3-yl, Δ³-1,2-dithiol-4-yl,            Δ³-1,2-dithiol-5-yl, 4,5-dihydro-1H-imidazol-2-yl,            4,5-dihydro-1H-imidazol-4-yl, 4,5-dihydro-1H-imidazol-5-yl,            2,5-dihydro-1H-imidazol-2-yl, 2,5-dihydro-1H-imidazol-4-yl,            2,5-dihydro-1H-imidazol-5-yl, 2,3-dihydro-1H-imidazol-2-yl,            2,3-dihydro-1H-imidazol-4-yl, 4,5-dihydrooxazol-2-yl,            4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl,            2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl,            2,5-dihydrooxazol-5-yl, 2,3-dihydrooxazol-2-yl,            2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl,            4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl,            4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl,            2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl,            2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl,            2,3-dihydrothiazol-5-yl, 1,3-dioxol-2-yl, 1,3-dioxol-4-yl,            1,3-dithiol-2-yl, 1,3-dithiol-4-yl, 1,3-oxathiol-2-yl,            1,3-oxathiol-4-yl, 1,3-oxathiol-5-yl, pyrazol-3-yl,            pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl,            isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,            imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl,            oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,            1,2,3-Δ²-oxadiazolin-4-yl, 1,2,3-Δ²-oxadiazolin-5-yl,            1,2,4-Δ⁴-oxadiazolin-3-yl, 1,2,4-Δ⁴-oxadiazolin-5-yl,            1,2,4-Δ²-oxadiazolin-3-yl, 1,2,4-Δ²-oxadiazolin-5-yl,            1,2,4-Δ³-oxadiazolin-3-yl, 1,2,4-Δ³-oxadiazolin-5-yl,            1,3,4-Δ²-oxadiazolin-2-yl, 1,3,4-Δ²-oxadiazolin-5-yl,            1,3,4-Δ³-oxadiazolin-2-yl, 1,3,4-oxadiazolin-2-yl,            1,2,4-Δ⁴-thiadiazolin-3-yl, 1,2,4-Δ⁴-thiadiazolin-5-yl,            1,2,4-Δ³-thiadiazolin-3-yl, 1,2,4-Δ³-thiadiazolin-5-yl,            1,2,4-Δ²-thiadiazolin-3-yl, 1,2,4-Δ²-thiadiazolin-5-yl,            1,3,4-Δ²-thiadiazolin-2-yl, 1,3,4-Δ²-thiadiazolin-5-yl,            1,3,4-Δ³-thiadiazolin-2-yl, 1,3,4-thiadiazolin-2-yl,            1,3,2-di-oxathiolan-4-yl, 1,2,3-Δ²-triazolin-4-yl,            1,2,3-Δ²triazolin-5-yl, 1,2,4-Δ²-triazolin-3-yl,            1,2,4-Δ²triazolin-5-yl, 1,2,4-Δ³-triazolin-3-yl,            1,2,4-Δ³triazolin-5-yl, 1,2,4-Δ¹-triazolin-2-yl,            1,2,4-triazolin-3-yl, 3H-1,2,4-dithiazol-5-yl,            2H-1,3,4-dithiazol-5-yl, 2H-1,3,4-oxathiazol-5-yl,            1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl,            1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,            1,3,4-oxadiazol-2-yl, 1,2,3-thiadiazol-4-yl,            1,2,3-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl,            1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl,            1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, tetrazol-5-yl;    -   C-bonded 6-membered rings, such as:        -   tetrahydropyran-2-yl, tetrahydropyran-3-yl,            tetrahydropyran-4-yl, piperidin-2-yl, piperidin-3-yl,            piperidin-4-yl, tetrahydrothiopyran-2-yl,            tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl,            2H-3,4-dihydropyran-6-yl, 2H-3,4-dihydropyran-5-yl,            2H-3,4-dihydropyran-4-yl, 2H-3,4-dihydropyran-3-yl,            2H-3,4-dihydropyran-2-yl, 2H-3,4-dihydropyran-6-yl,            2H-3,4-dihydrothiopyran-5-yl, 2H-3,4-dihydrothiopyran-4-yl,            2H-3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl,            1,2,3,4-tetrahydropyridin-6-yl,            1,2,3,4-tetrahydropyridin-5-yl,            1,2,3,4-tetrahydropyridin-4-yl,            1,2,3,4-tetrahydropyridin-3-yl,            1,2,3,4-tetrahydropyridin-2-yl, 2H-5,6-dihydropyran-2-yl,            2H-5,6-dihydropyran-3-yl, 2H-5,6-dihydropyran-4-yl,            2H-5,6-dihydropyran-5-yl, 2H-5,6-dihydropyran-6-yl,            2H-5,6-dihydrothiopyran-2-yl, 2H-5,6-dihydrothiopyran-3-yl,            2H-5,6-dihydrothiopyran-4-yl, 2H-5,6-dihydrothiopyran-5-yl,            2H-5,6-dihydrothiopyran-6-yl,            1,2,5,6-tetrahydropyridin-2-yl,            1,2,5,6-tetrahydropyridin-3-yl,            1,2,5,6-tetrahydropyridin-4-yl,            1,2,5,6-tetrahydropyridin-5-yl,            1,2,5,6-tetrahydropyridin-6-yl,            2,3,4,5-tetrahydropyridin-2-yl,            2,3,4,5-tetrahydropyridin-3-yl,            2,3,4,5-tetrahydropyridin-4-yl,            2,3,4,5-tetrahydropyridin-5-yl,            2,3,4,5-tetrahydropyridin-6-yl, 4H-pyran-2-yl,            4H-pyran-3-yl, 4H-pyran-4-yl, 4H-thiopyran-2-yl,            4H-thiopyran-3-yl, 4H-thiopyran-4-yl,            1,4-dihydropyridin-2-yl, 1,4-dihydropyridin-3-yl,            1,4-dihydropyridin-4-yl, 2H-pyran-2-yl, 2H-pyran-3-yl,            2H-pyran-4-yl, 2H-pyran-5-yl, 2H-pyran-6-yl,            2H-thiopyran-2-yl, 2H-thiopyran-3-yl, 2H-thiopyran-4-yl,            2H-thiopyran-5-yl, 2H-thiopyran-6-yl,            1,2-dihydropyridin-2-yl, 1,2-dihydropyridin-3-yl,            1,2-dihydropyridin-4-yl, 1,2-dihydropyridin-5-yl,            1,2-dihydropyridin-6-yl, 3,4-dihydropyridin-2-yl,            3,4-dihydropyridin-3-yl, 3,4-dihydropyridin-4-yl,            3,4-dihydropyridin-5-yl, 3,4-dihydropyridin-6-yl,            2,5-dihydropyridin-2-yl, 2,5-dihydropyridin-3-yl,            2,5-dihydropyridin-4-yl, 2,5-dihydropyridin-5-yl,            2,5-dihydropyridin-6-yl, 2,3-dihydropyridin-2-yl,            2,3-dihydropyridin-3-yl, 2,3-dihydropyridin-4-yl,            2,3-dihydropyridin-5-yl, 2,3-dihydropyridin-6-yl,            pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 1,3-dioxan-2-yl,            1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl,            1,3-dithian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5-yl,            1,4-dithian-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl,            1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl,            1,4-oxathian-3-yl, 1,2-dithian-3-yl, 1,2-dithian-4-yl,            hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl,            hexahydropyrimidin-5-yl, hexahydropyrazin-2-yl,            hexahydropyridazin-3-yl, hexahydropyridazin-4-yl,            tetrahydro-1,3-oxazin-2-yl, tetrahydro-1,3-oxazin-4-yl,            tetrahydro-1,3-oxazin-5-yl, tetrahydro-1,3-oxazin-6-yl,            tetrahydro-1,3-thiazin-2-yl, tetrahydro-1,3-thiazin-4-yl,            tetrahydro-1,3-thiazin-5-yl, tetrahydro-1,3-thiazin-6-yl,            tetrahydro-1,4-thiazin-2-yl, tetrahydro-1,4-thiazin-3-yl,            tetrahydro-1,4-oxazin-2-yl, tetrahydro-1,4-oxazin-3-yl,            tetrahydro-1,2-oxazin-3-yl, tetrahydro-1,2-oxazin-4-yl,            tetrahydro-1,2-oxazin-5-yl, tetrahydro-1,2-oxazin-6-yl,            2H-5,6-dihydro-1,2-oxazin-3-yl,            2H-5,6-dihydro-1,2-oxazin-4-yl,            2H-5,6-dihydro-1,2-oxazin-5-yl,            2H-5,6-dihydro-1,2-oxazin-6-yl,            2H-5,6-dihydro-1,2-thiazin-3-yl,            2H-5,6-dihydro-1,2-thiazin-4-yl,            2H-5,6-dihydro-1,2-thiazin-5-yl,            2H-5,6-dihydro-1,2-thiazin-6-yl,            4H-5,6-dihydro-1,2-oxazin-3-yl,            4H-5,6-dihydro-1,2-oxazin-4-yl,            4H-5,6-dihydro-1,2-oxazin-5-yl,            4H-5,6-dihydro-1,2-oxazin-6-yl,            4H-5,6-dihydro-1,2-thiazin-3-yl,            4H-5,6-dihydro-1,2-thiazin-4-yl,            4H-5,6-dihydro-1,2-thiazin-5-yl,            4H-5,6-dihydro-1,2-thiazin-6-yl,            2H-3,6-dihydro-1,2-oxazin-3-yl,            2H-3,6-dihydro-1,2-oxazin-4-yl,            2H-3,6-dihydro-1,2-oxazin-5-yl,            2H-3,6-dihydro-1,2-oxazin-6-yl,            2H-3,6-dihydro-1,2-thiazin-3-yl,            2H-3,6-dihydro-1,2-thiazin-4-yl,            2H-3,6-dihydro-1,2-thiazin-5-yl,            2H-3,6-dihydro-1,2-thiazin-6-yl,            2H-3,4-dihydro-1,2-oxazin-3-yl,            2H-3,4-dihydro-1,2-oxazin-4-yl,            2H-3,4-dihydro-1,2-oxazin-5-yl,            2H-3,4-dihydro-1,2-oxazin-6-yl,            2H-3,4-dihydro-1,2-thiazin-3-yl,            2H-3,4-dihydro-1,2-thiazin-4-yl,            2H-3,4-dihydro-1,2-thiazin-5-yl,            2H-3,4-dihydro-1,2-thiazin-6-yl,            2,3,4,5-tetrahydropyridazin-3-yl,            2,3,4,5-tetrahydropyridazin-4-yl,            2,3,4,5-tetrahydropyridazin-5-yl,            2,3,4,5-tetrahydropyridazin-6-yl,            3,4,5,6-tetrahydropyridazin-3-yl,            3,4,5,6-tetrahydropyridazin-4-yl,            1,2,5,6-tetrahydropyridazin-3-yl,            1,2,5,6-tetrahydropyridazin-4-yl,            1,2,5,6-tetrahydropyridazin-5-yl,            1,2,5,6-tetrahydropyridazin-6-yl,            1,2,3,6-tetrahydropyridazin-3-yl,            1,2,3,6-tetrahydropyridazin-4-yl,            4H-5,6-dihydro-1,3-oxazin-2-yl,            4H-5,6-dihydro-1,3-oxazin-4-yl,            4H-5,6-dihydro-1,3-oxazin-5-yl,            4H-5,6-dihydro-1,3-oxazin-6-yl,            4H-5,6-dihydro-1,3-thiazin-2-yl,            4H-5,6-dihydro-1,3-thiazin-4-yl,            4H-5,6-dihydro-1,3-thiazin-5-yl,            4H-5,6-dihydro-1,3-thiazin-6-yl,            3,4,5,6-tetrahydropyrimidin-2-yl,            3,4,5,6-tetrahydropyrimidin-4-yl,            3,4,5,6-tetrahydropyrimidin-5-yl,            3,4,5,6-tetrahydropyrimidin-6-yl,            1,2,3,4-tetrahydropyrazin-2-yl,            1,2,3,4-tetrahydropyrazin-5-yl,            1,2,3,4-tetrahydropyrimidin-2-yl,            1,2,3,4-tetrahydropyrimidin-4-yl,            1,2,3,4-tetrahydropyrimidin-5-yl,            1,2,3,4-tetrahydropyrimidin-6-yl,            2,3-dihydro-1,4-thiazin-2-yl, 2,3-dihydro-1,4-thiazin-3-yl,            2,3-dihydro-1,4-thiazin-5-yl, 2,3-dihydro-1,4-thiazin-6-yl,            2H-1,2-oxazin-3-yl, 2H-1,2-oxazin-4-yl, 2H-1,2-oxazin-5-yl,            2H-1,2-oxazin-6-yl, 2H-1,2-thiazin-3-yl,            2H-1,2-thiazin-4-yl, 2H-1,2-thiazin-5-yl,            2H-1,2-thiazin-6-yl, 4H-1,2-oxazin-3-yl, 4H-1,2-oxazin-4-yl,            4H-1,2-oxazin-5-yl, 4H-1,2-oxazin-6-yl, 4H-1,2-thiazin-3-yl,            4H-1,2-thiazin-4-yl, 4H-1,2-thiazin-5-yl,            4H-1,2-thiazin-6-yl, 6H-1,2-oxazin-3-yl, 6H-1,2-oxazin-4-yl,            6H-1,2-oxazin-5-yl, 6H-1,2-oxazin-6-yl, 6H-1,2-thiazin-3-yl,            6H-1,2-thiazin-4-yl, 6H-1,2-thiazin-5-yl,            6H-1,2-thiazin-6-yl, 2H-1,3-oxazin-2-yl, 2H-1,3-oxazin-4-yl,            2H-1,3-oxazin-5-yl, 2H-1,3-oxazin-6-yl, 2H-1,3-thiazin-2-yl,            2H-1,3-thiazin-4-yl, 2H-1,3-thiazin-5-yl,            2H-1,3-thiazin-6-yl, 4H-1,3-oxazin-2-yl, 4H-1,3-oxazin-4-yl,            4H-1,3-oxazin-5-yl, 4H-1,3-oxazin-6-yl, 4H-1,3-thiazin-2-yl,            4H-1,3-thiazin-4-yl, 4H-1,3-thiazin-5-yl,            4H-1,3-thiazin-6-yl, 6H-1,3-oxazin-2-yl, 6H-1,3-oxazin-4-yl,            6H-1,3-oxazin-5-yl, 6H-1,3-oxazin-6-yl, 6H-1,3-thiazin-2-yl,            6H-1,3-thiazin-4-yl, 6H-1,3-thiazin-5-yl,            6H-1,3-thiazin-6-yl, 2H-1,4-oxazin-2-yl, 2H-1,4-oxazin-3-yl,            2H-1,4-oxazin-5-yl, 2H-1,4-oxazin-6-yl, 2H-1,4-thiazin-2-yl,            2H-1,4-thiazin-3-yl, 2H-1,4-thiazin-5-yl,            2H-1,4-thiazin-6-yl, 4H-1,4-oxazin-2-yl, 4H-1,4-oxazin-3-yl,            4H-1,4-thiazin-2-yl, 4H-1,4-thiazin-3-yl,            1,4-dihydropyridazin-3-yl, 1,4-dihydropyridazin-4-yl,            1,4-dihydropyridazin-5-yl, 1,4-dihydropyridazin-6-yl,            1,4-dihydropyrazin-2-yl, 1,2-dihydropyrazin-2-yl,            1,2-dihydropyrazin-3-yl, 1,2-dihydropyrazin-5-yl,            1,2-dihydropyrazin-6-yl, 1,4-dihydropyrimidin-2-yl,            1,4-dihydropyrimidin-4-yl, 1,4-dihydropyrimidin-5-yl,            1,4-dihydropyrimidin-6-yl, 3,4-dihydropyrimidin-2-yl,            3,4-dihydropyrimidin-4-yl, 3,4-dihydropyrimidin-5-yl,            3,4-dihydropyrimidin-6-yl, pyridazin-3-yl, pyridazin-4-yl,            pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl,            pyrazin-2-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl,            1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl or            1,2,4,5-tetrazin-3-yl;    -   N-bonded 5-membered rings, such as:        -   tetrahydropyrrol-1-yl, 2,3-dihydro-1-H-pyrrol-1-yl,            2,5-dihydro-1-H-pyrrol-1-yl, pyrrol-1-yl,            tetrahydropyrazol-1-yl, tetrahydroisoxazol-2-yl,            tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl,            tetrahydrooxazol-3-yl, tetrahydrothiazol-3-yl,            4,5-dihydro-1H-pyrazol-1-yl, 2,5-dihydro-1H-pyrazol-1-yl,            2,3-dihydro-1H-pyrazol-1-yl, 2,5-dihydroisoxazol-2-yl,            2,3-dihydroisoxazol-2-yl, 2,5-dihydroisothiazol-2-yl,            2,3-dihydroisoxazol.-2-yl, 4,5-dihydro-1-H-imidazol-1-yl,            2,5-dihydro-1H-imidazol-1-yl, 2,3-dihydro-1H-imidazol-1-yl,            2,3-dihydrooxazol-3-yl, 2,3-dihydrothiazol-3-yl,            pyrazol-1-yl, imidazol-1-yl, 1,2,4-Δ⁴-oxadiazolin-2-yl,            1,2,4-Δ²-oxadiazolin-4-yl, 1,2,4-Δ³-oxadiazolin-2-yl,            1,3,4-Δ²-oxadiazolin-4-yl, 1,2,4-Δ⁵-thiadiazolin-2-yl,            1,2,4-Δ³-thiadiazolin-2-yl, 1,2,4-Δ²-thiadiazolin-4-yl,            1,3,4-Δ²-thiadiazolin-4-yl, 1,2,3Δ²-triazolin-1-yl,            1,2,4-Δ²-triazolin-1-yl, 1,2,4-Δ²-triazolin-4-yl,            1,2,4-Δ³-triazolin-1-yl, 1,2,4-Δ¹-triazolin-4-yl,            1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, tetrazol-1-yl;    -   N-bonded 6-membered rings, such as:        -   piperidin-1-yl, 1,2,3,4-tetrahydropyridin-1-yl,            1,2,5,6-tetrahydropyridin-1-yl, 1,4-dihydropyridin-1-yl,            1,2-dihydropyridin-1-yl, hexahydropyrimidin-1-yl,            hexahydropyrazin-1-yl, hexahydropyridazin-1-yl,            tetrahydro-1,3-oxazin-3-yl, tetrahydro-1,3-thiazin-3-yl,            tetrahydro-1,4-thiazin-4-yl, tetrahydro-1,4-oxazin-4-yl            (morpholinyl), tetrahydro-1,2-oxazin-2-yl,            2H-5,6-dihydro-1,2-oxazin-2-yl,            2H-5,6-dihydro-1,2-thiazin-2-yl,            2H-3,6-dihydro-1,2-oxazin-2-yl,            2H-3,6-dihydro-1,2-thiazin-2-yl,            2H-3,4-dihydro-1,2-thiazin-2-yl,            2,3,4,5-tetrahydropyridazin-2-yl,            1,2,5,6-tetrahydropyridazin-1-yl,            1,2,5,6-tetrahydropyridazin-2-yl,            1,2,3,6-tetrahydropyridazin-1-yl,            3,4,5,6-tetrahydropyrimidin-3-yl,            1,2,3,4-tetrahydropyrazin-1-yl,            1,2,3,4-tetrahydropyrimidin-1-yl,            1,2,3,4-tetrahydropyrimidin-3-yl,            2,3-dihydro-1,4-thiazin-4-yl, 2H-1,2-oxazin-2-yl,            2H-1,2-thiazin-2-yl, 4H-1,4-oxazin-4-yl,            4H-1,4-thiazin-4-yl, 1,4-dihydropyridazin-1-yl,            1,4-dihydropyrazin-1-yl, 1,2-dihydropyrazin-1-yl,            1,4-dihydropyrimidin-1-yl or 3,4-dihydropyrimidin-3-yl;    -   and N-bonded cyclic imides, such as:        -   phthalimide, tetrahydrophthalimide, succinimide, maleimide,            glutarimide, 5-oxotriazolin-1-yl,            5-oxo-1,3,4-oxadiazolin-4-yl or            2,4-dioxo-(1H,3H)-pyrimidin-3-yl;        -   where heterocyclyl may, together with a fused-on phenyl ring            or with a C₃-C₆-carbocycle or with a further 5- or            6-membered heterocycle, form a bicyclic ring system,        -   where one ring carbon in the heterocycle may be present as            carbonyl or thiocarbonyl group,        -   where the sulfur of the heterocycles mentioned may be            oxidized to S═O or S(═O)₂.

Unless indicated otherwise, all phenyl rings or heterocyclyl radicalsand all phenyl components in phenoxy, phenylalkyl, phenylamino,phenylcarbonyl, phenyloxycarbonyl, phenylaminocarbonyl andN-alkyl-N-phenylaminocarbonyl, and all heterocyclyl components inheterocyclyloxy, heterocyclylalkyl, heterocyclylcarbonyl,heterocyclyloxycarbonyl, heterocyclylcarbonyloxy are preferablyunsubstituted or are partially or fully halogenated and/or carry one,two or three substituents selected from the group consisting of nitro,cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,C₃-C₆-cycloalkylamino, where the alkyl and cycloalkyl groups of thethree last-mentioned radicals may be partially or fully halogenatedand/or may carry one to three substituents selected from the groupconsisting of C₁-C₄-alkoxy and hydroxyl.

For the reaction of the aryl halides II with the compounds III or III′or III″, preference is given to those transition metal catalysts whoseactive metal component comprises at least one platinum metal and inparticular a transition metal selected from the group consisting ofpalladium, platinum, nickel, cobalt, ruthenium and rhodium. Particularpreference is given to those catalysts which comprise palladium as metalof group VIII of the Periodic Table of the Elements.

The catalysts, in particular those which comprise platinum, nickel,cobalt, ruthenium and rhodium and in particular palladium ascatalytically active metal, can be employed as metals or in the form ofcustomary salts, for example in the form of halogen compounds, such asPdCl₂, NiCl₂, CoCl₂, RhCl₃.H₂O, acetates, such as Pd(OAc)₂, Co(OAc)₂,acetylacetonates or cyanides, in the known valence states.

Moreover, the catalytically active metals can be employed in the form ofmetal complexes, for example with tertiary phosphines, as metal alkylcarbonyls, mixed complexes which comprise at least two differentligands, preferably at least one tertiary phosphine and at least oneligand different therefrom, for example CO, or with transition metalsalts complexed with tertiary phosphines.

For the process according to the invention, it has been found to beuseful for the catalyst system to comprise, in addition to thetransition metal of group VIII of the Periodic Table, a tertiaryphosphine, where the tertiary phosphine can be added to the reactionmixture separately or together with the transition metal in the form ofa transition metal complex.

Suitable phosphine ligands can be represented, for example, by theformulae below:

in which A is a divalent organic radical, for example C₁-C₆—, preferablyC₁-C₄-alkanediyl, in particular 1,2-ethylene or 1,3-propylene,1,2-cycloalkanediyl, for example 1,2-cyclohexanediyl,1,2-cyclopentanediyl, ferrocenediyl, a polycyclic aromatic radical, suchas 1,8-anthracenediyl, or a 2,2-biphenyl structure.

The radicals R^(x), R^(y), R^(x′), R^(y′) are, independently of oneanother, C₁-C₆-alkyl, C₅-C₈-cycloalkyl, such as cyclohexyl, aryl, inparticular phenyl or p-tolyl, C₁-C₄-alkylaryl, for example benzyl,phenethyl, or aryloxy, such as phenoxy. R^(x), R^(y), R^(x′), R^(y′) arepreferably aryl. Aryl is, for example, phenyl, naphthyl, anthryl, whichmay be substituted or unsubstituted, and is in particular unsubstitutedor substituted phenyl, such as tolyl. With respect to the substituentson aryl, attention has to be paid primarily to their inertness to thereaction conditions used. Suitable radicals are all inert C-organicradicals, such as C₁-C₆-alkyl radicals, for example methyl, sulfonyl orcarboxyl radicals, such as COOH, COOM (M is, for example, an alkalimetal, alkaline earth metal or an ammonium salt), or C-organic radicalswhich are attached via oxygen, such as C₁-C₆-alkoxy radicals.

Examples of such complexes are P(C₆H₅)₃, P(C₆H₄CH₃)₃, P(n-C₄H₉)₃,P(cyclo-C₆H₁₁)₃, PCH₃(C₆H₅)₂, 1,2-bis(diphenylphosphino)ethane,1,3-bis(diphenylphosphino)propane, 1,8-bis(diphenylphosphino)anthraceneand α,α′-bis(diphenylphosphino)ferrocene. A particularly preferredtertiary phosphine is triarylphosphine and in particulartriphenylphosphine, which may be substituted on the phenyl ring.

Examples of complex compounds which are preferred according to theinvention are (PPh₃)₂Ni(CO)₂, Pt(CO)₂(PPh₃)₂, in particularPd(CO)(PPh₃)₃, (PPh₃)₂Pd(OAc)₂, (PPh₃)₂PdCl₂.

The phosphine complexes can be prepared in a manner known per se. Thestarting material used is, for example a customary commerciallyavailable metal salt, such as PdCl₂ or Pd(OCOCH₃)₂, and the phosphine,for example P(C₆H₅)₃, P(C₆H₄CH₃)₃, P(n-C₄H₉)₃, P(cyclo-C₆H₁₁)3,PCH₃(C₆H₅)₂, 1,2-bis(diphenylphosphino)ethane,1,3-bis(diphenylphosphino)propane, 1,8-bis(diphenylphosphino)anthraceneor α,α′-bis(diphenylphosphinoferrocene, is added, if appropriate in asolvent. Frequently, the complexes are also generated in situ in thereaction mixture by adding at least one phosphine ligand and a precursorcompound, i.e. a transition metal compound which comprises thecatalytically active metal, for example a metal salt or another complexof the metal, to the reaction mixture.

If the ligand used in the process according to the invention is aphosphine, the amount of phosphine, based on one mole of transitionmetal, is at least 0.1 mol, preferably at least 0.5 mol and particularlypreferably at least 1 mol. In general, the molar ratio of tertiaryphosphine to transition metal will not be above 20, preferably 10 and inparticular 5, not least in order to keep the input of foreign substancesinto reaction components II and III as low as possible.

The catalysts can be employed as such or on a support. The nature of thesupport is not crucial. Suitable supports include inorganic oxides, suchas silicon dioxide, alumina, alumosilicates, for example zeolites,calcium carbonate, barium sulfate, furthermore activated carbon, carbonblack. Suitable support materials are furthermore organic polymers, inparticular those which are capable of complexing the transition metal,for example polymers having tertiary amino groups, pyridine groups,imidazole groups or polymers having tertiary phosphine groups.

The amount of transition metal is not critical. Obviously, for costreasons, the use of a small amount, for example from 0.1 to 20 mol %, inparticular from 0.5 to 10 mol %, based on the aryl halide II, will bepreferred. It is, of course, also possible to use relatively largeamounts, for example 50, 100 or 200 mol %, based on 1 mole of arylhalide II.

Suitable for the process according to the invention are all inert basescapable of binding the hydrogen halide, in particular hydrogen bromide,released during the reaction. Examples of suitable bases are amines,preferably tertiary amines, in particular trialkylamines, such astriethylamine, triethanolamine, cyclic amines, such asN-methylpiperidine, triethylenediamine(=1,4-diazabicyclo[2.2.2]octane),1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene orN,N′-dimethylpiperazine, heteroaromatic amines, such as pyridine andsubstituted pyridines, furthermore alkali metal carbonates orbicarbonates, or tetraalkyl-substituted urea derivatives, such astetra-C₁-C₄-alkylurea, for example tetramethylurea.

The amount of base is not critical; usually, the base will be employedin an amount of at least one mole per mole of aryl halide II, forexample in an amount of from 1 to 10 mole, in particular from 1 to 5mole. It is, of course, also possible to use the base as solvent ordiluent for the reactants. If the base is simultaneously used assolvent, the amount is generally such that the reaction partners aredissolved, unnecessarily high excesses being avoided for reasons ofpracticability in order to save costs, to be able to employ smallreaction vessels and to ensure that the reaction partners have maximumcontact.

However, depending on the nature of the starting materials and thecatalyst used, it may be advantageous to use an inert solvent differentfrom the reaction partner or the base.

Suitable inert solvents are, for example, aromatic hydrocarbons, such astoluene, xylenes, cumene, aliphatic hydrocarbons, such as hexane,pentane or cyclohexane, halogenated aliphatic hydrocarbons, such asdichloromethane, trichloromethane, carbon tetrachloride,1,2-dichloroethane and 1,1-dichloroethane, ethers, such as methyltert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substitutedamides, such as dimethylformamide or N-methylpyrrolidone, persubstitutedureas, such as tetra-C₁-C₄-alkylureas, or nitrites, such as benzonitrileor acetonitrile, and also mixtures of the solvents mentioned above.Preferred solvents are aromatic hydrocarbons or solvent mixturescontaining a high proportion of aromatic hydrocarbons.

Furthermore, it is found to be useful to carry out the process accordingto the invention in the presence of lithium ions. Suitable sources oflithium are, in particular, lithium salts, such as lithium halides, forexample lithium chloride, furthermore basic lithium salts, such aslithium carbonate, lithium acetate or lithium hydroxide. In thesepreferred embodiments of the process according to the invention, ingeneral from 0.1 to 10 mol, in particular from 0.2 to 5 mol andparticularly preferably from 0.5 to 2 mol of lithium ions are employedper mole of aryl halide.

In the process according to the invention, aryl halide II and thecompounds III or III′ or III″ are generally employed in approximatelystoichiometric amounts, an excess of one of the components of up to 50mol %, based on the component which is present in substoichiometricamounts, generally not having any negative effect. The diketone III orits tautomer III′ or III″ is preferably employed in an approximatelyequimolar amount, or in excess.

During the reaction, the carbon monoxide pressure is adjusted such thatthere is always an excess of carbon monoxide, based on the aryl halide.The carbon monoxide partial pressure at room temperature is preferablyfrom 1 to 250 bar, in particular from 5 to 150 bar, CO.

The process according to the invention is generally carried out attemperatures of from room temperature to 300° C., preferably at 50-250°C., in particular at 100-200° C., continuously or batchwise. If theprocess is carried out batchwise, it is expedient, in order to maintaina constant pressure, to continuously introduce pressurized carbonmonoxide into the reaction mixture.

The process according to the invention can be applied to a large numberof different substrate compounds II and III. In the formula II, Hal ispreferably bromine or iodine and in particular bromine.

Aryl halides II which may be mentioned are, for example, compounds whichare represented by the formula IIa

in which Hal is chlorine, bromine or iodine, preferably bromine oriodine and in particular bromine and Hal is preferably adjacent to theradical R^(1a), and

-   R^(1a) and R^(4a) independently of one another are hydrogen,    halogen, in particular fluorine, chlorine, cyano, C₁-C₆-alkyl,    C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio,    C₁-C₆-haloalkylthio, hydroxy-C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl,    C₁-C₆-haloalkylsulfonyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,    C₁-C₆-alkylthio-C₁-C₆-alkyl, C₁-C₆-haloalkylthio-C₁-C₆-alkyl,    C₁-C₆-alkylsulfonyl-C₁-C₆-alkyl,    C₁-C₆-haloalkylsulfonyl-C₁-C₆-alkyl, C₁-C₆-alkylamino-C₁-C₆-alkyl,    or di(C₁-C₆-alkyl)amino-C₁-C₆-alkyl and-   R^(2a) and R^(3a) form a 5- or 6-membered saturated or unsaturated    heterocycle which may have 1, 2 or 3 heteroatoms selected from the    group consisting of N, S and O, where    -   sulfur atoms in the heterocycle may also be present as sulfoxide        or sulfone,    -   nitrogen atoms and carbon atoms in the heterocycle have a        hydrogen atom or a substituent selected from the group        consisting of halogen, nitro, cyano, hydroxy, amino,        C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-aminoalkyl,        hydroxy-C₁-C₆-alkyl C₁-C₆-alkylcarbonyl, C₁-C₆-alkylcarbonyloxy,        C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,        C₁-C₆-alkylcarbonyl-C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,        C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-hydroxyalkoxy,        C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₃-C₆-cycloalkyl, C₃-C₈-cycloalkoxy,        C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-hydroxyalkylthio,        C₁-C₆-alkoxy-C₁-C₆-alkylthio,    -   phenyl, phenyl-C₁-C₆-alkyl, phenylcarbonyl, phenylcarbonyloxy,        phenoxycarbonyl, 5-, 6- or 7-membered heterocyclyl, phenoxy,        phenylamino, diphenylamino, heterocyclyl-C₁-C₆-alkyl,        heterocyclyloxy, heterocyclylcarbonyl, heterocyclyloxycarbonyl,        heterocyclylcarbonyloxy, where the phenyl and heterocyclyl        groups of the 14 last-mentioned radicals may for their part be        partially of fully halogenated and/or may carry one, two or        three substituents selected from the group consisting of nitro,        cyano, hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and        C₁-C₄-haloalkoxy, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,        C₃-C₆-cycloalkylamino, where the alkyl and cycloalkyl groups of        the three last-mentioned radicals may be partially or fully        halogenated and/or may carry one to three substituents selected        from the group consisting of C₁-C₄-alkoxy or hydroxyl,    -   where carbon ring members may also be present as carbonyl        function, thiocarbonyl function, oxime or oxime ether function;        or-   R^(1a) and R^(2a) or R^(3a) and R^(4a) form a fused 5- or 6-membered    saturated or unsaturated heterocycle which may have 1, 2 or 3    heteroatoms selected from the group consisting of N, S and O, where    the ring atoms of the heterocycle may be substituted in the manner    described above; and    -   the remaining radicals R^(1a), R^(2a), R^(3a) and R^(4a)        independently of one another have the meanings mentioned for        R^(1a), or-   R^(2a) is hydrogen or fused 5-, 6- or 7-membered heterocyclyl which    has 1, 2 or 3 hetero atoms selected from the group consisting of N,    S and O, where the ring atoms of the heterocycle may be substituted    in the manner described above; and-   R^(1a), R^(3a) and R^(4a) independently of one another have the    meanings mentioned above for R^(1a).

Fused 5- or 6-membered heterocycles which may be mentioned are, forexample, pyrrole, 2,3-dihydropyrrole, 2,5-dihydropyrrole, pyrazole,2,3-dihydropyrazole, imidazole, 2,3-dihydroimidazole, triazole, furan,2,3- and 2,5-dihydrofuran, oxazole, 2,3-dihydrooxazole, isoxazole,2,3-dihydroisoxazole, thiophene, 2,3- and 2,5-dihydrothiophene, thiazol,2,3-dihydrothiazole, isothiazole, 2,3-dihydroisothiazole, pyridine,1,2-, 2,3- and 3,4-dihydropyrimidine and tetrahydropyridine. Fusedcarbocycles are, for example, cyclopentene, cyclopentadiene,cyclohexene, cyclohexadiene, benzene, cycloheptene.

Thus, for example, R^(1a) and R^(2a) or R^(3a) and R^(4a) form, togetherwith the benzene ring to which they are attached, an indole, isoindole,benzofuran, isobenzofuran, benzo-[a]-thiophene benzo-[b]-thiophene,benzimidazole, benzoxazole, benzothiazole, benzisothiazole,benzotriazole, quinoline, isoquinoline, quinoxaline, chromane,thiochromane, chromene, thiochromen, indane, indene or naphthalene ring,or a derivative thereof which is partially hydrogenated on the fusedring.

The heterocyclic structures may, of course, also be partiallyhydrogenated, and the N and/or C ring atoms may be substituted in themanner described above. Carbon ring members can also be present ascarbonyl function, thiocarbonyl function, oxime or oxime-ether function,as in chroman-4-one, thiochroman-4-one, benzoisothiazolone, and ringsulfur atoms may be present as sulfoxide or sulfone, such asbenzothiophene S-oxide, benzothiophene S,S-dioxide, benzothiazoleS-oxide, benzothiazole S,S-dioxide, thiochromane S-oxide andthiochromane S,S-dioxide.

In a preferred embodiment of the process according to the invention,aryl halides of the formula IIb are employed:

in which Hal is as defined above and R^(1b) and R^(4b) have the meaningsgive above for R^(1a) and R^(4a), respectively, Hal is preferablyadjacent to R^(1b), R^(1b) is preferably halogen, in particular fluorineor chlorine, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy andC₁-C₄-haloalkoxy, R^(4b) is preferably hydrogen, fluorine, chlorine,methyl or methoxy,

-   R^(5b) is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,    C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₁-C₆-hydroxyalkoxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy,    C₃-C₈-cycloalkyl, phenyl, phenyl-C₁-C₆-alkyl, where phenyl in the    two last-mentioned groups may carry one, two or three substituents    selected from the group consisting of halogen, nitro, cyano,    hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and    C₁-C₄-haloalkoxy, and is in particular C₁-C₄-alkyl, phenyl or    phenyl-C₁-C₄-alkyl, where phenyl may be unsubstituted or substituted    in the manner described above.-   n is 0, 1 or 2 and-   X is oxygen or sulfur, in particular oxygen.

In a further preferred embodiment of the process according to theinvention, aryl halides of the formula IIc are employed

in which Hal is as defined above and is preferably adjacent to R^(1c),R^(1c) has the meanings given for R^(1a) and is preferably halogen, inparticular fluorine or chlorine, C₁-C₄-alkyl, in particular methyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy,

-   R^(3c) is halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylthio,    C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkoxy or    C₁-C₆-haloalkoxy, and in particular C₁-C₆-alkylsulfonyl and    especially chlorine, fluorine, methyl, methoxy or methylsulfonyl,-   is a double bond or preferably a single bond and-   R^(6c) is hydrogen or unsubstituted or substituted C₁-C₄-alkyl. In    this context, substituted C₁-C₄-alkyl is preferably haloalkyl as    defined above, for example fluoromethyl, chloromethyl,    difluoromethyl, chlorodifluoromethyl or trifluoromethyl, or    C₁-C₄-alkoxy-C₁-C₄-alkyl as defined above, for example    methoxymethyl.

In a further preferred embodiment of the process according to theinvention, aryl halides of the formula IId are employed

in which Hal is as defined above and is preferably adjacent to R^(1d),R^(1d) has the meanings mentioned for R^(1a) and is preferably halogen,and in particular fluorine or chlorine, C₁-C₄-alkyl, in particularmethyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy,

-   R^(3d) is halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylthio,    C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkoxy or    C₁-C₆-haloalkoxy and in particular C₁-C₆-alkylsulfonyl and    especially chlorine, fluorine, methyl, methoxy or methylsulfonyl.

The compound II used in the process according to the invention may, ofcourse, also be an unsubstituted halobenzene, such as bromobenzene, or ahalopyridine, such as 2-, 3- or 4-bromopyridine.

The 1,3-diketone of the formula III (or the tautomer III′ or III″) usedin the process according to the invention is preferably a cyclic orbicyclic 1,3-diketone of the formula IIIa or IIIb:

in which k is 0, 1 or 2 and the variables R¹ to R⁶ as defined below:

-   R¹, R⁵ independently of one another are hydrogen, C₁-C₄-alkyl, in    particular methyl, or C₁-C₄-alkoxycarbonyl;-   R², R⁴, R⁶ independently of one another are hydrogen, C₁-C₄-alkyl,    in particular methyl, C₁-C₄-alkoxy such as methoxy or    C₁-C₄-alkylthio such as methylthio;-   R³ is hydrogen, halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl,    di(C₁-C₆-alkoxy)methyl, (C₁-C₆-alkoxy)-(C₁-C₆-alkylthio)methyl,    di(C₁-C₆-alkylthio)methyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,    C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl,    C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl,    C₁-C₆-haloalkylsulfonyl, C₁-C₆-alkoxycarbonyl,    C₁-C₆-haloalkoxycarbonyl; in particular, hydrogen or methyl    -   1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl,        1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where        the six last-mentioned radicals may be substituted by one to        three C₁-C₄-alkyl radicals; or-   R² and R⁴ or R⁴ and R⁶ together form a π bond or a C₁-C₅-alkanediyl    chain which may have a π bond and/or may carry one, two or three    radicals from the following group: halogen, cyano, C₁-C₄-alkyl,    C₁-C₄-haloalkyl or C₁-C₄-alkoxycarbonyl; or-   R⁵ and R⁶ together form a C₁-C₅-alkanediyl chain which may have a π    bond and/or may carry one, two or three radicals from the following    group: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl or    C₁-C₄-alkoxycarbonyl; or-   R² and R⁶ together form a C₁-C₄-alkanediyl chain which may have a π    bond and/or may carry one, two or three radicals from the following    group: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl or    C₁-C₄-alkoxycarbonyl, which is preferably unsubstituted; or-   R³ and R⁴ together form a chain of the formula —O—(CH₂)_(p)—O—,    —O—(CH₂)_(p)—S—, —S—(CH₂)_(p)—S—, —O—(CH₂)_(q)— or —S—(CH₂)_(q)—, in    which p is 2, 3, 4 or 5 preferably 2 or 3 and q is 2, 3, 4, 5 or 6    and which may be substituted by one, two or three radicals from the    following group: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl or    C₁-C₄-alkoxycarbonyl and is preferably unsubstituted; or-   R³ and R⁴ together with the carbon to which they are attached form a    carbonyl or thiocarbonyl group.

Examples of preferred cyclic diketones of the formula IIIa or IIIb arethe cyclohexane 1,3-diones of the formulae III-1 to III-12:

Work-up of the reaction according to the invention of aryl halide IIwith 1,3-diketone III can be carried out in a manner known per se. Thereaction mixture can, for example, be evaporated to dryness, preferablyunder reduced pressure. In general, the residue is then recrystallizedfrom a suitable solvent and/or purified chromatographically, where thesolvent used for recrystallization and the stationary phase and themobile phase (eluent) used for chromatography do, of course, depend onthe nature of the starting material and can be determined in a simplemanner by a person skilled in the art using standard tests. In manycases, silica or alumina is a suitable stationary phase. Suitableeluents are, for example, aliphatic and cycloaliphatic hydrocarbons,such as n-hexane or cyclohexane, or mixtures thereof with polarsolvents, such as ethers, or esters, for example ethyl acetate. It is,of course, also possible to work-up the reaction mixture by aqueousextraction, to remove salts, for example acid addition salts formedduring the reaction, of hydrogen halide and the base that is employed,or catalysts.

The process according to the invention affords the β-ketoenol esters ofthe formula I in good yields. The great advantage of the process is inparticular the fact that, in place of the aryl carboxylic acids AR—COOH,some of which are difficult to prepare, it is possible to use the arylhalides of the formula II, which are easier to obtain.

The β-Ketoenol esters of the formula I which can be obtained by theprocess according to the invention are generally rearranged in asubsequent reaction by treatment of I with a base and a catalyticallyeffective amount of at least one cyanide compound, to give the2-aryl-substituted 1,3-diketones of the formula X. To this end, theβ-Ketoenol esters I can be used as isolated pure substance, as isolatedcrude product of the reaction described above or in the reaction mixtureof the reaction described above, without prior isolation. The reactionmixture obtained by the process according to the invention can, forexample, be admixed directly, after removal of the carbon monoxide, witha base and a catalytically effective amount of at least one cyanidecompound, whereby the rearrangement of I into the compound X isinitiated.

Rearrangement of the β-ketoenol esters I into the compounds of theformula X is generally carried out at 20-100° C. in a solvent and in thepresence of a base and, if appropriate, using a cyano compound ascatalyst.

Suitable for use as solvents are, for example, acetonitrile, methylenechloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene ormixtures of these. Preferred solvents are acetonitrile and dioxane, andmixtures thereof.

Suitable bases are the tertiary amines mentioned above, such astriethylamine and pyridine, alkaline earth metal or alkali metalcarbonates, such as sodium carbonate or potassium carbonate, which arepreferably employed in an equimolar amount or an up to four-fold excess,based on the β-Ketoenol ester of the formula I. Preference is given tousing triethylamine or alkali metal carbonate, preferably in twice theequimolar ratio, based on the ester.

Suitable for use as cyano compounds are, for example, inorganiccyanides, such as sodium cyanide or potassium cyanide, and organic cyanocompounds which can release cyanide ions, for example cyanohydrins ofaliphatic ketones, which is acetone-cyanohydrin, or trialkylsilylcyanides, such as trimethylsilyl cyanide. They are preferably employedin an amount of from 1 to 50 mol percent, in particular 5 to 25 mol %,based on the β-ketoenol ester I. Preference is given to using acetonecyanohydrin or trimethylsilyl cyanide, for example in an amount of from5 to 25, preferably about 10 to 20, mol percent, based on the β-ketoenolester I.

Work-up can be carried out in a manner known per se. The reactionmixture of the rearrangement is, for example, acidified with dilutemineral acid, for example 5% strength hydrochloric acid or sulfuricacid, and extracted with an organic solvent, for example methylenechloride or ethyl acetate. To remove impurities, the organic extract canbe extracted with a base, such as 5-10% strength alkali metal carbonatesolution, for example sodium carbonate or potassium carbonate solution.The aqueous phase is acidified and the resulting precipitate is filteredoff with suction and/or extracted with methylene chloride or ethylacetate, the extract being dried and concentrated. If appropriate, theresidue is recrystallized and/or further purified chromatographically,in the manner described above.

The examples below serve to illustrate the invention in more detail.

I. β-Ketonenol ester

General procedure for the reaction of 5-bromo-2,4-dimethylsaccharin(5-bromo-2,4-dimethyl-1,2-benzoisothiazol-3(2H)-one 1,1-dioxide=compoundof the formula IIb where R^(1b)=R^(5b)=methyl, R^(4b)=hydrogen, X=0, n=2and Hal=bromine) with cyclohexan-1,3-dionenes of the formula IIIa in alaboratory autoclave (Examples 1 to 3).

1 g (3.6 mmol) of 5-bromo-2,4-dimethylsaccharin, 4.3 mmol (1.2 eq.) of1,3-diketone, 0.1 g of bis(triphenylphosphine)palladium dichloride, 0.15g (3.6 mmol) of lithium chloride and 0.73 g (7.2 mmol) of triethylaminewere initially charged in 100 ml of solvent in a laboratory autoclave.The gas space of the autoclave was then flushed 1 to 6 times with carbonmonoxide, the autoclave was heated to 140° C. and a carbon monoxidepressure of 20 bar was then applied. Temperature and pressure weremaintained for 12 to 24 h, and the autoclave was then cooled and ventedto atmospheric pressure and the reaction mixture was concentrated todryness.

For work-up according to Method A, the residue was chromatographed onsilica gel using a cyclohexane/ethyl acetate gradient (100/0 to 60/40v/v).

For work-up according to method B, the residue was taken up in ethylacetate and washed three times with 5% by weight strength aqueous sodiumcarbonate, twice with 10% by weight strength hydrochloric acid and twicewith water. The organic phase was dried over sodium carbonate andconcentrated to dryness under reduced pressure.

In each case, the respective β-ketoenol ester of2,4-dimethylsaccharin-5-carboxylic acid was obtained as a viscous oil oras a white solid.

The authenticity of the resulting compounds was checked by ¹H-NMRspectrum. The starting materials and results of the reaction are givenin Table 1.

TABLE 1 Yield Example Diketone Solvent Work-up [%]¹⁾ 1 III-9 Toluene A17.6 2 III-4 Toluene B 77.7 3 III-4 Dioxane B 63 ¹⁾Based on5-bromo-2,4-dimethylsaccharine

EXAMPLE 4

10 g (36 mmol) of 5-bromo-2,4-dimethylsaccharine, 5 g (36 mmol) ofbicyclo[3.2.1]-1,3-dioxooctane (diketone III-4), 1 g ofbis(triphenylphosphine)palladium dichloride, 1.5 g (3.6 mmol) of lithiumchloride and 7.3 g (72 mmol) of triethylamine were initially charged in700 ml of toluene in a 1-1-autoclave and inertized. The gas space of theautoclave was then flushed with carbon monoxide, the autoclave washeated to 140° C. and a carbon monoxide pressure of 20 bar was applied.Temperature and pressure were maintained for 24 h, and the autoclave wasthen cooled and vented to atmospheric pressure.

For work-up, the reaction mixture was washed 3 times each with 5% byweight strength aqueous sodium carbonate, 10% by weight strengthhydrochloric acid and water. The organic phase was dried over sodiumsulfate and evaporated to dryness under reduced pressure. This gave 10.4g of5-[(bicyclo[3.2.1]-3-oxoocten-1-yl)oxycarbonyl]-2,4-dimethylsaccharin asa viscous oil.

EXAMPLE 5

In the presence of bis(triphenylphosphine)palladium dichloride, lithiumchloride and triethylamine, 1-bromo-2,4-dichlorobenzene and4,4,6,6-tetramethyl-1,3,5-trioxocyclohexane (diketone III-2) werereacted in the manner and the ratios described for Example 4. This gave,after work-up,(4,4,6,6-tetramethyl-3,5-dioxo-cyclohexen-1-yl)-2,4-dichloro-benzoate ina yield of 30%.

EXAMPLE 6

In the presence of bis(triphenylphosphine)palladium dichloride, lithiumchloride and triethylamine, 1-bromo-2,4-dichlorobenzene and4,6-dimethyl-1,3-dioxocyclohexane (diketone III-3) were reacted in themanner and the ratios described for Example 4. This gave, after work-up,(4,6-dimethyl-3-dioxocyclohex-1-ene-1-yl)-2,4-dichlorobenzoate in ayield of 27%.

EXAMPLE 8

In the presence of bis(triphenylphosphine)palladium dichloride, lithiumchloride and triethylamine,1-bromo-2-methyl-4-methylsulfonyl-3-(4′-5′-dihydrooxazol-3-yl)benzeneand (36 mmol) 5,5-dimethyl-1,3-dioxocyclohexan (diketone III-9) werereacted in the manner and the ratios described for example 4. This gave,after work-up,1-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)oxycarbonyl-2-methyl-4-methylsulfonyl-3-(4′,5′-dihydrooxazol-3-yl)benzenein a yield of 35%.

EXAMPLE 9

In the presence of bis(triphenylphosphine)palladium dichloride, lithiumchloride and triethylamine,1-bromo-2-methyl-4-methylsulfonyl-3-(4′-5′-dihydrooxazol-3-yl)benzeneand cyclohexan-1,3-dione (diketone III-1) were reacted in the manner andthe ratios described for Example 4. This gave, after work-up,1-(3-oxocyclohex-1-en-1-yl)oxycarbonyl-2-methyl-4-methylsulfonyl-3-(4′,5′-dihydrooxazol-3-yl)benzene.

In the manner descried in Examples 8 and 9, it is furthermore possibleto prepare the β-ketoenol esters of the formula below

where Hex, R^(1c) and R^(3c) are each as defined in Table 2. Hex is oneof the cyclohexenone radicals Hex-1 to Hex-5 defined below

TABLE 2 Example Hex R^(1c) R^(3c) 8 Hex-5 CH₃ SO₂CH₃ 9 Hex-1 CH₃ SO₂CH₃10 Hex-5 F Cl 11 Hex-5 F F 12 Hex-5 F OCH₃ 13 Hex-5 F CH₃ 14 Hex-5 FSO₂CH₃ 15 Hex-5 CH₃ Cl 16 Hex-5 CH₃ F 17 Hex-5 CH₃ OCH₃ 18 Hex-5 CH₃ CH₃19 Hex-5 OCH₃ Cl 20 Hex-5 OCH₃ F 21 Hex-5 OCH₃ OCH₃ 22 Hex-5 OCH₃ CH₃ 23Hex-5 OCH₃ SO₂CH₃ 24 Hex-5 Cl Cl 25 Hex-5 Cl F 26 Hex-5 Cl OCH₃ 27 Hex-5Cl CH₃ 28 Hex-5 Cl SO₂CH₃ 29 Hex-1 F Cl 30 Hex-1 F F 31 Hex-1 F OCH₃ 32Hex-1 F CH₃ 33 Hex-1 F SO₂CH₃ 34 Hex-1 CH₃ Cl 35 Hex-1 CH₃ F 36 Hex-1CH₃ OCH₃ 37 Hex-1 CH₃ CH₃ 38 Hex-1 OCH₃ Cl 39 Hex-1 OCH₃ F 40 Hex-1 OCH₃OCH₃ 41 Hex-1 OCH₃ CH₃ 42 Hex-1 OCH₃ SO₂CH₃ 43 Hex-1 Cl Cl 44 Hex-1 Cl F45 Hex-1 Cl OCH₃ 46 Hex-1 Cl CH₃ 47 Hex-1 Cl SO₂CH₃ 48 Hex-2 F Cl 49Hex-2 F F 50 Hex-2 F OCH₃ 51 Hex-2 F CH₃ 52 Hex-2 F SO₂CH₃ 53 Hex-2 CH₃Cl 54 Hex-2 CH₃ F 55 Hex-2 CH₃ OCH₃ 56 Hex-2 CH₃ CH₃ 57 Hex-2 CH₃ SO₂CH₃58 Hex-2 OCH₃ Cl 59 Hex-2 OCH₃ F 60 Hex-2 OCH₃ OCH₃ 61 Hex-2 OCH₃ CH₃ 62Hex-2 OCH₃ SO₂CH₃ 63 Hex-2 Cl Cl 64 Hex-2 Cl F 65 Hex-2 Cl OCH₃ 66 Hex-2Cl CH₃ 67 Hex-2 Cl SO₂CH₃ 68 Hex-3 F Cl 69 Hex-3 F F 70 Hex-3 F OCH₃ 71Hex-3 F CH₃ 72 Hex-3 F SO₂CH₃ 73 Hex-3 CH₃ Cl 74 Hex-3 CH₃ F 75 Hex-3CH₃ OCH₃ 76 Hex-3 CH₃ CH₃ 77 Hex-3 CH₃ SO₂CH₃ 78 Hex-3 OCH₃ Cl 79 Hex-3OCH₃ F 80 Hex-3 OCH₃ OCH₃ 81 Hex-3 OCH₃ CH₃ 82 Hex-3 OCH₃ SO₂CH₃ 83Hex-3 Cl Cl 84 Hex-3 Cl F 85 Hex-3 Cl OCH₃ 86 Hex-3 Cl CH₃ 87 Hex-3 ClSO₂CH₃ 88 Hex-4 F Cl 89 Hex-4 F F 90 Hex-4 F OCH₃ 91 Hex-4 F CH₃ 92Hex-4 F SO₂CH₃ 93 Hex-4 CH₃ Cl 94 Hex-4 CH₃ F 95 Hex-4 CH₃ OCH₃ 96 Hex-4CH₃ CH₃ 97 Hex-4 CH₃ SO₂CH₃ 98 Hex-4 OCH₃ Cl 99 Hex-4 OCH₃ F 100 Hex-4OCH₃ OCH₃ 101 Hex-4 OCH₃ CH₃ 102 Hex-4 OCH₃ SO₂CH₃ 103 Hex-4 Cl Cl 104Hex-4 Cl F 105 Hex-4 Cl OCH₃ 106 Hex-4 Cl CH₃ 107 Hex-4 Cl SO₂CH₃II. 2-Aroyl-1,3-diketones

The rearrangement of the compounds prepared under I can be carried out,for example, according to Example C) 17, p. 19 of WO 96/05182, which isexpressly incorporated herein by way of reference.

1. A process for preparing β-ketoenol esters of the formula Ia or Ib

in which R^(a), R^(b) independently of one another are C₁-C₆-alkyl orC₃-C₈-cycloalkyl, or R^(a) and R^(b) together are C₂-C₄-alkanediyl orC₅-C₇-cycloalkanediyl, where the three groups mentioned above may besubstituted or unsubstituted and may have a fused 3-, 4-, 5- or6-membered saturated carbocycle, a spiro-linked 3-, 4-, 5- or 6- or7-membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or7-membered saturated heterocycle having 1 or 2 chalkogen atoms, selectedfrom the group consisting of oxygen and sulfur and/or a carbonyl orthiocarbonyl group; Ar is phenyl or pyridyl, which may in each case have1, 2, 3 or 4 substituents, it also being possible for two substituentsattached to adjacent carbon atoms to form, together with these atoms, a5- or 6-membered saturated or unsaturated carbocycle or a 5- or6-membered saturated or unsaturated heterocycle which has 1, 2 or 3hetero atoms selected from the group consisting of O, N and S and whichfor its part may be substituted or unsubstituted; which comprisesreacting an aryl halide of the formula IIAr-Hal  (II) in which Hal is bromine with a 1,3-diketone of the formulaIII or its tautomer III′ or III″

in a carbon monoxide atmosphere in the presence of a base and a catalystwhich comprises at least one transition metal of group VIII of thePeriodic Table of the Elements.
 2. A process as claimed in claim 1,wherein the catalyst comprises the transition metal palladium.
 3. Aprocess as claimed in claim 1, wherein the catalyst additionallycomprises a tertiary phosphine.
 4. A process as claimed in claim 3,wherein the tertiary phosphine is a triarylphosphine.
 5. A process asclaimed in claim 1, wherein the base is selected from secondary andtertiary amines.
 6. A process as claimed in claim 1, wherein thereaction is carried out at a temperature in the range from 50 to 250° C.7. A process as claimed in claim 1, wherein the 1,3-diketone of theformula III or its tautomers III′ and III″ are of the formula IIIa orIIIb:

in which k is 0, 1 or 2 and the variables R¹ to R⁶ are as defined below:R¹, R⁵ independently of one another are hydrogen, C₁-C₄-alkyl orC₁-C₄-alkoxycarbonyl; R², R⁴, R⁶ independently of one another arehydrogen, C₁-C₄-alkyl, C₁-C₄-alkylthio or C₁-C₄-alkoxy; R³ is hydrogen,halogen, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, di(C₁-C₆-alkoxy)methyl,(C₁-C₆-alkoxy)(C₁-C₆-alkylthio)methyl, di(C₁-C₆-alkylthio)methyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl,C₁-C₆-haloalkylsulfonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆-haloalkoxycarbonyl;1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl,1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the sixlast mentioned radicals may be substituted by one to three C₁-C₄-alkylradicals; or R² and R⁴ or R⁴ and R⁶ together form a π bond or aC₁-C₅-alkanediyl chain which may have a π bond and/or may carry one, twoor three radicals from the following group: halogen, cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl or C₁-C₄-alkoxycarbonyl; or R⁵ and R⁶ together form aC₁-C₅-alkanediyl chain which may have a π bond and/or may carry one, twoor three radicals from the following group: halogen, cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl or C₁-C₄-alkoxycarbonyl; or R² and R⁶ together form aC₁-C₄-alkanediyl chain which may have a π bond and/or may carry one, twoor three radicals from the following group: halogen, cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl or C₁-C₄-alkoxycarbonyl; or R³ and R⁴ together form achain of the formula —O—(CH₂)_(p)—O—, —O—(CH₂)_(p)—S—, —S—(CH₂)_(p)—S—,—O—(CH₂)_(q)— or —S—(CH₂)_(q)—, in which p is 2, 3, 4 or 5 and q is 2,3, 4, 5 or 6 and which may be substituted by one, two or three radicalsfrom the following group: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkylor C₁-C₄-alkoxycarbonyl; or R³ and R⁴ together with the carbon to whichthey are attached form a carbonyl or thiocarbonyl group.
 8. A process asclaimed in claim 1, wherein the aryl halide of the formula II isrepresented by the formula IIa:

in which R^(1a) and R^(4a) independently of one another are hydrogen,halogen, in particular fluorine or chlorine, cyano, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio,C₁-C₆-haloalkylthio, hydroxy-C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl,C₁-C₆-haloalkylsulfonyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,C₁-C₆-alkylthio-C₁-C₆-alkyl, C₁-C₆-haloalkylthio-C₁-C₆-alkyl,C₁-C₆-alkylsulfonyl-C₁-C₆-alkyl, C₁-C₆-haloalkylsulfonyl-C₁-C₆-alkyl,C₁-C₆-alkylamino-C₁-C₆-alkyl, or di(C₁-C₆-alkyl)amino-C₁-C₆-alkyl andR^(2a) and R^(3a) form a 5- or 6-membered saturated or unsaturatedheterocycle which may have 1, 2 or 3 heteroatoms selected from the groupconsisting of N, S and O, where sulfur atoms in the heterocycle may alsobe present as sulfoxide or sulfone, nitrogen atoms and carbon atoms inthe heterocycle have a hydrogen atom or a substituent selected from thegroup consisting of halogen, nitro, cyano, hydroxyl, amino, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-aminoalkyl, C₁-C₆-alkylcarbonyl,C₁-C₆-alkylcarbonyloxy, C₁-C₆-alkyloxycarbonyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylcarbonyl-C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-hydroxyalkoxy,C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₃-C₆-cycloalkyl, C₃-C₈-cycloalkoxy,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-hydrokyalkylthio,C₁-C₆-alkoxy-C₁-C₆-alkylthio, phenyl, phenyl-C₁-C₆-alkyl,phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, 5-, 6- or 7-memberedheterocyclyl, phenoxy, phenylamino, diphenylamino,heterocyclyl-C₁-C₆-alkyl, heterocyclyloxy, heterocyclylcarbonyl,heterocyclyloxycarbonyl, heterocyclylcarbonyloxy, where the phenyl andheterocyclyl groups of the 14 last-mentioned radicals may for their partbe partially of fully halogenated and/or may carry one, two or threesubstituents selected from the group consisting of nitro, cyano,hydroxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy andC₁-C₄-haloalkoxy, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,C₃-C₆-cycloalkylamino, where the alkyl and cycloalkyl groups of thethree last-mentioned radicals may be partially or fully halogenatedand/or may carry one to three substituents selected from the groupconsisting of C₁-C₄-alkoxy or hydroxyl, where carbon ring members mayalso be present as carbonyl function, thiocarbonyl function, oxime oroxime ether function; or R^(1a) and R^(2a) or R^(3a) and R^(4a) form a5- or 6-membered saturated or unsaturated heterocycle which may have 1,2 or 3 heteroatoms selected from the group consisting of N, S and O,where the ring atoms of the heterocycle may be substituted in the mannerdescribed above; and the remaining radicals R^(1a), R^(2a), R^(3a) andR^(4a) independently of one another have the meanings mentioned forR^(1a), or R^(2a) is hydrogen or 5-, 6- or 7-membered heterocyclyl whichhas 1, 2 or 3 hetero atoms selected from the group consisting of N, Sand O, where the ring atoms of the heterocycle may be substituted in themanner described above; and R^(1a), R^(3a) and R^(4a) independently ofone another have the meanings mentioned above for R^(1a).
 9. A processas claimed in claim 8, wherein the aryl halide II is represented by theformula IIb:

in which Hal is as defined above and R^(1b) and R^(4b) have the meaningsmentioned above for R^(1a) and R^(4a), respectively, R^(5b) is hydrogen,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₁-C₆-hydroxyalkoxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₃-C₈-cycloalkyl,phenyl, phenyl-C₁-C₆-alkyl, where phenyl in the two last-mentionedgroups may carry one, two or three substituents selected from the groupconsisting of halogen, nitro, cyano, hydroxyl, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy, n is 0, 1 or 2 and Xis oxygen or sulfur.
 10. A process as claimed in claim 8, wherein thearyl halide II is represented by the formula IIc:

in which Hal is as defined above and R^(1c) has the meanings given forR^(1a), R^(3c) is halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkoxyor C₁-C₆-haloalkoxy, is a double bond or a single bond and R^(6c) ishydrogen or C₁-C₄-alkyl.
 11. A process as claimed in claim 8, whereinthe aryl halide II is represented by the formula IId:

in which Hal is as defined above and R^(1d) has the meanings mentionedfor R^(1a) and R^(3d) is halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkoxyor C₁-C₆-haloalkoxy.
 12. A process for preparing 2-aroyl-substituted1,3-diketones of the formula X or their tautomer Xa, Xb or Xc

in which R^(a), R^(b), and Ar are as defined in claim 1, which comprisesthe following reaction steps:
 1. Reaction of a 1,3-diketone of theformula III defined in claim 1 or its tautomers III′ or III″ with anaryl halide Ar-Hal in which Hal is chlorine, bromine or iodine in acarbon monoxide atmosphere in the presence of a base and a transitionmetal catalyst which comprises at least one transition metal of groupVIII of the Periodic Table of the Elements to give a β-ketoenol ester ofthe formula Ia or Ib defined in claim 1 and,
 2. rearrangement of thecompound Ia or Ib to give a compound X or Xa, Xb and/or Xc by treatmentof Ia and/or Ib with a base and a catalytically effective amount of atleast one cyanide compound.